Int. J. Mol. Sci. 2014, 15, 20254-20265; doi:10.

3390/ijms151120254
OPEN ACCESS

International Journal of

Molecular Sciences
ISSN 1422-0067
www.mdpi.com/journal/ijms
Article

Formation and Yield of Multi-Walled Carbon Nanotubes

Synthesized via Chemical Vapour Deposition Routes Using
Different Metal-Based Catalysts of FeCoNiAl, CoNiAl
and FeNiAl-LDH
Mohd Zobir Hussein 1,*, Adila Mohamad Jaafar 1,2,, Asmah Hj. Yahaya 2,,
Mas Jaffri Masarudin 3, and Zulkarnain Zainal 2,
1

Advanced Material and Nanotechnology Laboratory, Institute of Advanced Technology (ITMA),

Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia;
E-Mail: adilamj@upm.edu.my
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang,
Selangor, Malaysia; E-Mails: hamsajaya@upm.edu.my (A.H.Y.); zulkar@upm.edu.my (Z.Z.)
Department of Cell and Molecular Biology, Faculty of Biotechnology and Biomolecular Sciences,
Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia;
E-Mail: masjaffri@upm.edu.my
These authors contributed equally to this work.

* Author to whom correspondence should be addressed; E-Mail: mzobir@upm.edu.my;

Tel.: +603-8946-8092; Fax: +603-8946-7006.
External Editor: Andreas Taubert
Received: 2 July 2014; in revised form: 14 October 2014 / Accepted: 23 October 2014 /
Published: 5 November 2014

Abstract: Multi-walled carbon nanotubes (MWCNTs) were prepared via chemical vapor
deposition (CVD) using a series of different catalysts, derived from FeCoNiAl, CoNiAl
and FeNiAl layered double hydroxides (LDHs). Catalyst-active particles were obtained by
calcination of LDHs at 800 C for 5 h. Nitrogen and hexane were used as the carrier gas and
carbon source respectively, for preparation of MWCNTs using CVD methods at 800 C.
MWCNTs were allowed to grow for 30 min on the catalyst spread on an alumina boat in a
quartz tube. The materials were subsequently characterized through X-ray diffraction,
Fourier transform infrared spectroscopy, surface area analysis, field emission scanning
electron microscopy and transmission electron microscopy. It was determined that size and

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yield of MWCNTs varied depending on the type of LDH catalyst precursor that is used
during synthesis. MWCNTs obtained using CoNiAl-LDH as the catalyst precursor showed
smaller diameter and higher yield compared to FeCoNiAl and FeNiAl LDHs.
Keywords: chemical vapor deposition; layered double hydroxides; hexane; MWCNTs

1. Introduction
Layered double hydroxides (LDHs), also variedly known as anionic clays, can be structurally
described as stacks of positively charged layers intercalated with anions within its inter-spacing. The
structure of LDHs follows that of brucite-like layers, in which a divalent metal cation is located within
the center of an oxygen octahedra, and two-dimensional infinite layers are formed through edge
sharing of the octahedra. The partial isomorphous substitution of trivalent cations for divalent cations
results in a net positive charge of the layers. Conferment of a positive charge allows for any organic or
inorganic anions to be readily intercalated between the brucite layers, in order to maintain a structural
charge balance. Often, water molecules arising from the crystallization process also associates within
these interlayer galleries. LDHs classes of materials generally follow a chemical formula representing
of [MII1x MIIIx (OH)2]b+ [Amb/m].nH2O, where M (II) is a divalent cation, M (III) is a trivalent cation
and A is an anion with charge of n [1].
The interlayer spacing of LDH has been shown to provide for a potent reactive environment, even
in gentle thermal treatments. Calcination reactions at intermediate temperatures (450600 C) showed
persistence of the layered brucite, but subsequently collapsed at significantly higher temperatures.
Calcined LDH products often exist in the form of mixed metal oxides. During LDH calcination under
inert gas environments, both spinel M(II)M(III)2O4 and free M(II)O are frequently produced. Mixed
metal oxides have attracted an appreciable research fascination, both as catalysts and catalyst supports,
due to their high metal dispersion, and stable-supported metal particles, which possess both basic
and acidic group sites. The mixed oxide catalysts obtained by thermal decomposition of LDHs also
confer advantageous modifications of enhanced surface areas, thus creating active sites for reactions to
readily occur with the possibility of higher percentage product outputs [1].
Since its discovery by Iijima in 1991, carbon nanotubes (CNT) have garnered great interest in
material science research, both from a fundamental perspective, as well as its potential for various
practical applications. CNTs are versatile nanosized structures, with unique electronic, mechanical,
optical, and chemical characteristics that pave the way towards a myriad of potential interdisciplinary
applications. These types of materials have been especially studied for applications in transistors,
field-emission tips, sensors, supercapacitors and in the biomedical field [26]. Apart from electric-arc
discharge and laser ablation techniques, carbon nanotubes can also be prepared through catalytic
pyrolysis of carbon-containing gases via catalytic chemical vapor deposition (CCVD) [7]. The CCVD
technique has been widely explored in the production of several CNT, such as single-walled,
double-walled, and multi-walled derivatives [810]. Concurrently, efforts have now focused towards
the determination of optimal catalysts for efficient nanotube fabrication, which mostly consists of Fe,

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Co, Ni elements over porous material supports, or high-surface-area oxide matrices that increase their
reactivity as catalyst clusters [1114].
The successful application of metal oxides catalyst derived from LDH-based materials have
attracted its application in the synthesis of CNT formation through carbon vapor deposition routes.
Recently, the efficacy of LDHs as catalyst precursors for the synthesis of carbon nanotubes via
catalytic chemical vapor deposition of acetylene has been reported. Nanometer-sized cobalt particles
were prepared by the calcination and subsequent reduction of a single LDH precursor containing
cobalt (II) and aluminum ions homogeneously dispersed at the atomic level. The Co nanoparticles have
been employed as catalytically active sites for growth of CNTs. Multi-walled carbon nanotubes
(MWCNTs) with uniform diameters were obtained [15]. Enhanced catalytic activities can be observed
by incorporating transition metal cations into the brucite-like layers of LDHs, contributed by the
unique properties of the final catalysts, such as high metal dispersion and large surface area after a
controlled thermal treatment. Better control in the dispersion and size of the catalyst particles is also
achieved, through the ordered prearrangement of metal cations in the layers of the LDH precursor at an
atomic level.
This study reports the application of three metal-based catalysts; FeCoNiAl-DH, CoNiAl-LDH,
and FeNiAl-LDH for use in the formation of CNTs. The preparation of CNTs via use of LDH-based
catalysts confers the advantage of low synthesis temperatures using cheap, simple instrumentation, and
a robust prospective for large-scale productions. Here, FeCoNiAl-DH, CoNiAl-LDH, and FeNiAl-LDH
previously prepared at the fixed ratio of R = 4 was initially prepared via co-precipitation methods.
The resulting FeCoNiAl, CoNiAl, and FeNiAl composite oxides were then obtained by calcination of
corresponding LDH precursors at 800 C, and were then used as catalyst or substrate in the formation
of carbon nanotubes. The influence of these three types of material towards growth of CNTs was then
examined and visualized via various means of physiochemical analyses.
2. Results and Discussion
2.1. Carbon Yield
The catalytic activity of CoNiAl, FeNiAl and FeCoNiAl mixed oxide catalyst were tested in hexane
decomposition at a reaction temperature of 800 C. As expected, different mixed oxide catalysts
notably affected carbon yield. Carbon yields of 183.5%, 124.8%, and 110.5% were obtained for
synthesized CoNiAl-CNT, FeCoNiAl-CNT and FeNiAl-CNT, respectively.
2.2. Powder X-ray Diffraction
Figure 1a shows the x-ray diffraction (XRD) patterns of the catalysts CoNiAl-LDH, FeCoNiAl-LDH,
and FeNiAl-LDH precursors. Characteristic reflections corresponding to hydrotalcite-like LDHs were
observed in all three samples, indicating a potent formation of brucite structures. Other crystalline
phases non-indicative of the LDH structure were not detected. The narrow and sharp reflections
observed had suggested that the LDH products confer good crystallinity and structural integrity.
However, XRD patterns of LDH samples following calcination (Figure 1b) did not show these

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characteristic reflections, which indicates an absence of the layered structure of LDHs. This observation
was expected, due to the collapse of the LDH metal layers after thermal treatment.
The use of the LDH precursors with uniformly distributed cations seemed to facilitate the formation
of spinel phases [16]. However, it is difficult to distinguish the different phases, due to its superposition
of characteristic reflections in the XRD spectras. The position and relative intensity of the reflections
were basically identical for all samples. Powder x-ray diffraction (PXRD) patterns for synthesized
CNT materials are as shown in Figure 1c, where a peak centered at approximately 26.1 in all three
samples was determined as the reflection plane of graphite, thus confirming existence of a carbon
element [17] that is CNTs.
Figure 1. Powder X-ray diffraction (PXRD) patterns of layered double hydroxides (LDH)
(a) calcined LDH (b) and CNT over calcined LDH (c). Asterisks (*) show characteristic
peaks for LDH at 8.5 (003). Dots () indicate the characteristic peaks for carbon (26.1 ,
44.8 ), indicating the formation of CNT.

2.3. Fourier Transform Infrared

The Fourier Transform Infrared (FTIR) spectra in Figure 2a show the typical features of LDH with
carbonate as the anion in the interlayer. The FTIR analysis shows that the appearance of a broad band
at 32773388 cm1 corresponds to the O-H vibration mode, OH. At around 16301634 cm1, weak
bands could be observed which is attributed to the H2O. Strong peaks in the range of 13511360 cm1
correspond to the vibration of CO32. Sharp and strong bands located at less than 1000 cm1
correspond to MO vibrations and MOH bending [18,19]. Figure 2b shows that the O-H vibration mode
groups at 3409 cm1 had decreased in calcined CoNiAl material, and was absent in other calcined
samples. However, this O-H vibration mode peak intensity was still found uncalcined LDH, suggesting

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a dissociation of the LDH structure in calcined materials. The thermal treatment of LDHs has also
shown its effect on the CO32 vibration band which caused the band to decrease in size. As discussed
in the FTIR of LDHs, the bands at lower wavenumber are due to the vibrations of M-O, M-O-M, and
O-M-O bonds in the layers, which are typical for this kind of layered solids [20]. There are a few
infrared active modes of CNTs and it depends on the symmetry of the CNTs, which is chiral, zigzag
and armchair [21]. In Figure 2c, the features at 17391745 cm1 [22] and 15371541 cm1 [23,24] are
attributed to the MWCNT vibration modes. From the FTIR analysis, the CNTs were observed to exist in
the sample and this is in agreement with the PXRD analysis.
Figure 2. FTIR of LDH (a) calcined LDH (b) and CNT over calcined LDH (c).

2.4. Surface Area Analysis

From Figure 3, FeCoNiAl, CoNiAl and FeNiAl based material in the form of LDHs (a), calcined
LDHs (b) and CNTs (c) exhibited surface properties of Type IV isotherms which can be attributed by
the mesoporous-type structure (20500 ) [25]. All of the isotherms showed almost the same trend of
little difference being exhibited at low relative pressures. However, the slope increase at high relative
pressures indicates an increased uptake of adsorbate due to adsorption in mesopores, which leads
to multilayer formation until a certain pressure where condensation takes place. A very narrow H3
hysteresis loop could be observed at high pressures, which exhibit no limit to the adsorption at high
P/P [25]. All of the adsorption and desorption branches shown in Figure 3 are parallel except for
FeNiAl and FeCoNiAl-LDH which could be due to the complex pore structures. Figure 4ac showed
that the pore was distributed randomly at 190 nm in FeCoNiAl, CoNiAl and FeNiAl based material in
the form of LDHs, calcined LDHs and CNTs, respectively. Significant modifications in the pore size

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of CoNiAl based material could be observed as shown in Table 1. CoNiAl-CNT possesses the highest
BET surface area at 47.56 m2g1 and the smallest BJH desorption average pore diameter value of
0.98 nm, which could lead to the formation of carbon nanotubes with small diameters.
Figure 3. Adsorption-desorption isotherms of LDH (a) calcined LDH (b) and CNT over
calcined LDH (c).

Figure 4. Pore size distribution of LDH (a) calcined LDH (b) and CNT over calcined LDH (c).

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Table 1. Surface properties of FeNiAl, CoNiAl and FeCoNiAl LDH, calcined LDH and
CNT over calcined LDH.
Material
FeNiAl
LDH
FeCoNiAl
CoNiAl
FeNiAl
Calcined
FeCoNiAl
LDH
CoNiAl
FeNiAl
CNT
FeCoNiAl
CoNiAl

BET Surface Area (m2g1)

35.1
32.5
1.0
6.4
6.7
22.3
33.7
19.8
47.6

BJH Desorption Average Pore Diameter (nm)

5.3
8.0
39.0
10.7
8.9
1.6
1.2
1.6
0.98

2.5. Field Emission Scanning Electron Microscope

Figure 5 shows Field Emission Scanning Electron Microscope (FESEM) images of obtained CNTs
with various morphologies. As observed in Figure 5a, CoNiAl-CNT was found to be the smallest
diameter, followed by FeNiAl-CNT (Figure 5b) and FeCoNiAl-CNT (Figure 5c). Reasons leading to
the formation of different sized CNTs using different types of LDH might include the composition of
metal interaction in the layers and the distribution of metals when calcination took place. These have
an effect on the size of the metal catalyst, which influences the growth of carbon nanotubes [26].
CoNiAl-CNT produced had smooth surfaces, were long and straight, and entangled implying that the
synthesized CNTs are of good quality and well graphitized. Both FeNiAl-CNT and FeCoNiAl-CNT
display helical nanotubes with rough surface morphology. However, FeCoNiAl-CNT shows entanglement
of every part of the nanotubes.
2.6. Transmission Electron Microscope
Figure 6 shows Transmission Electron Microscope (TEM) observations of differences in the
structures of CNT when different mixed oxides as catalysts were used. CoNiAl-CNT in Figure 6a
exhibited CNTs entangled with each other and contained lower amounts of amorphous carbon on
their surfaces, indicating high quality CNTs. Both FeNiAl-CNT (Figure 6b) and FeCoNiAl-CNT
(Figure 6c) show defects such as kinks and bends in the tubes. The outer diameters of nanotubes are
shown in Figure 6, which exhibit diameters of 20.60, 27.08 and 43.87 nm for CoNiAl-, FeNiAl-CNT
and FeCoNiAl-CNT, respectively. As observed, Figures 5 and 6 complement each other. The size of
CoNiAl-CNT, which shows the smallest diameter, could be due to the stable active cobalt clusters,
impeding agglomeration among other particles and therefore leading to better dispersion of active
metal particles, which finally influence the formation of the CNTs [1,27]. Here, it is believed that the
difference in the diameters of CNTs grown with different types of metal catalysts is principally
attributed to the different agglomeration of existing metallic metal particles.

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Figure 5. Field Emission Scanning Electron Microscope (FESEM) micrograph of

CoNiAl-CNT (a); FeNiAl-CNT (b) and FeCoNiAl-CNT (c).

Figure 6. Transmission Electron Microscope (TEM) images of carbon nanotubes of

CoNiAl-CNT (a); FeNiAl-CNT (b) and FeCoNiAl-CNT (c).

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3. Experimental Section
3.1. Preparation of LDH Precursors
The LDHs of Co-Ni-Al-SO42 (CoNiAl), Fe-Ni-Al-SO42 (FeNiAl), and Fe-Co-Ni-Al-SO42
(FeCoNiAl) were synthesized through co-precipitation methods. The molar ratios of cobalt:aluminium,
nickel:aluminium, and iron:aluminium were set at 4:1. Mixed aqueous solutions of cobalt, nickel, iron,
and aluminium nitrates were prepared at pH 10.00 0.05 by dropwise addition of aqueous NaOH
solution (2.00 M) with vigorous stirring. The titration of NaOH was performed under the constant
flow of nitrogen gas to avoid, or at least minimize contamination by atmospheric CO2 throughout the
experiment. The precipitate was then aged at 70 C for 18 h, washed, and dried in the oven at 70 C.
The dried samples were then ground into fine powder by a mortar and pestle, before kept in sample
bottles pending further use and characterisation. The as-synthesized LDH samples were calcined in air
at 800 C for 5 h at a heating rate of 4 C/min. The resulting mixed metal oxides were then slowly
cooled to room temperature.
3.2. Growth of CNTs
CNTs were synthesized by catalytic chemical vapor deposition of hexane, in a quartz tube housed
inside a horizontal tube furnace equipped with gas flow controller and temperature-programmed
control. After loading the calcined LDH samples in an alumina boat, the temperature in the furnace
was raised from room temperature to 800 C at a rate of 4 C/min, under nitrogen gas flow at 50 PSIG
for 150 min. After 120 min hexane was introduced, and the temperature was maintained for a
subsequent 30 min before the whole system was turned off. The furnace was then left to cool to room
temperature. The resulting synthesized CNTs were kept in sample bottles pending further use and
characterisation. For calculation of percentage carbon yield, the following equation was used;
Carbon yield (%)

mass of carbon deposited onto the catalyst 100

initial mass of mixed oxide

3.3. Characterisation
Powder X-ray diffraction (PXRD) patterns of the samples were collected using an ITAL Structure
APD 2000 instrument. The CuK used was at the wavelength = 0.1540562 nm and scanning rate
was set at 2 degreesmin1. Infrared absorption spectras of each sample were analyzed in a FTIR
spectrophotometer in the form of KBr pellets, using a Perkin-Elmer model 1725X, in the wavelength
range of 4004000 cm1. The N2 adsorption-desorption isotherm, the specific surface area and pore
size distribution was carried out by using a BELSORP-mini. Before the analysis, the samples were
degassed at 105 C under vacuum environment. CARL ZEISS SUPRA 40VP operated at 5 kV was
used for field emission scanning electron microanalyses (FESEM) of the samples. Transmission
electron microscopy (TEM) images were taken using Hitachi H-7100 operated at 40 kV.

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4. Conclusions
Carbon nanotubes were grown on a series of catalysts derived from CoNiAl-LDH, FeCoNiAl-LDH
and FeNiAl-LDH materials. The catalytically active Co, Ni and Fe species for MWNTs growth were
successfully formed by calcination of LDHs at 800 C. Different mixed oxides catalyst precursors
were found to produce different carbon yields of CNTs, as well as different sizes and structure of
the formed MWNTs. CoNiAl mixed oxide was found to give the highest yield of CNTs with less
amorphous carbons on their wall surfaces, indicating high quality CNTs were produced.
Acknowledgments
The support of the research by MOHE under RUGS no. 02-11-08-615FR is gratefully acknowledged.
Adila Mohd Jaafar thanks UPM for PASCA Siswazah Scheme studentships and Mohd Zobir Hussein
thanks MOSTI for the Overseas Advanced Research Fellowship Scheme.
Author Contributions
Each author has contributed equally towards the experimental work and write-up of the manuscrip
for the study.
Conflicts of Interest
The authors declare no conflict of interest.
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